US5070141A - Polyacrylate graft-polyol dispersants - Google Patents
Polyacrylate graft-polyol dispersants Download PDFInfo
- Publication number
- US5070141A US5070141A US07/226,329 US22632988A US5070141A US 5070141 A US5070141 A US 5070141A US 22632988 A US22632988 A US 22632988A US 5070141 A US5070141 A US 5070141A
- Authority
- US
- United States
- Prior art keywords
- polyol
- dispersant
- weight percent
- stable
- polyacrylate graft
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920005862 polyol Polymers 0.000 title claims abstract description 272
- 239000002270 dispersing agent Substances 0.000 title claims abstract description 74
- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 55
- 150000003077 polyols Chemical class 0.000 claims abstract description 221
- 239000000178 monomer Substances 0.000 claims abstract description 75
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 31
- 229920000570 polyether Polymers 0.000 claims abstract description 31
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 28
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 24
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 18
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 229920000642 polymer Polymers 0.000 claims description 107
- 238000000034 method Methods 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 28
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 12
- 229920005903 polyol mixture Polymers 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- 125000005395 methacrylic acid group Chemical class 0.000 claims description 6
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical group CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 5
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 4
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000007348 radical reaction Methods 0.000 claims description 3
- 230000002708 enhancing effect Effects 0.000 claims description 2
- 238000005191 phase separation Methods 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 4
- 230000000087 stabilizing effect Effects 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 17
- 239000005056 polyisocyanate Substances 0.000 abstract description 17
- 229920001228 polyisocyanate Polymers 0.000 abstract description 17
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 229920002635 polyurethane Polymers 0.000 abstract description 6
- 239000004814 polyurethane Substances 0.000 abstract description 6
- 229920001577 copolymer Polymers 0.000 abstract description 5
- 239000002585 base Substances 0.000 description 18
- 229920005830 Polyurethane Foam Polymers 0.000 description 16
- 239000011496 polyurethane foam Substances 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- 239000006260 foam Substances 0.000 description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 12
- 239000003999 initiator Substances 0.000 description 12
- -1 ethyl propyl Chemical group 0.000 description 11
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 8
- 229920006389 polyphenyl polymer Polymers 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 235000011187 glycerol Nutrition 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 3
- 239000004604 Blowing Agent Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- XXROGKLTLUQVRX-UHFFFAOYSA-N hydroxymethylethylene Natural products OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 150000003440 styrenes Chemical class 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- ZWKNLRXFUTWSOY-QPJJXVBHSA-N (e)-3-phenylprop-2-enenitrile Chemical compound N#C\C=C\C1=CC=CC=C1 ZWKNLRXFUTWSOY-QPJJXVBHSA-N 0.000 description 2
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 description 2
- JLIDVCMBCGBIEY-UHFFFAOYSA-N 1-penten-3-one Chemical compound CCC(=O)C=C JLIDVCMBCGBIEY-UHFFFAOYSA-N 0.000 description 2
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- CJWBPEYRTPGWPF-UHFFFAOYSA-N 2-[bis(2-chloroethoxy)phosphoryloxy]ethyl bis(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCOP(=O)(OCCCl)OCCCl CJWBPEYRTPGWPF-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000003466 anti-cipated effect Effects 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- UIYCHXAGWOYNNA-UHFFFAOYSA-N vinyl sulfide Chemical compound C=CSC=C UIYCHXAGWOYNNA-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- HOVAGTYPODGVJG-UVSYOFPXSA-N (3s,5r)-2-(hydroxymethyl)-6-methoxyoxane-3,4,5-triol Chemical compound COC1OC(CO)[C@@H](O)C(O)[C@H]1O HOVAGTYPODGVJG-UVSYOFPXSA-N 0.000 description 1
- SHXHPUAKLCCLDV-UHFFFAOYSA-N 1,1,1-trifluoropentane-2,4-dione Chemical compound CC(=O)CC(=O)C(F)(F)F SHXHPUAKLCCLDV-UHFFFAOYSA-N 0.000 description 1
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- SIZPGZFVROGOIR-UHFFFAOYSA-N 1,4-diisocyanatonaphthalene Chemical compound C1=CC=C2C(N=C=O)=CC=C(N=C=O)C2=C1 SIZPGZFVROGOIR-UHFFFAOYSA-N 0.000 description 1
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 description 1
- UNMYKPSSIFZORM-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)butane Chemical compound CCCCOCCOC=C UNMYKPSSIFZORM-UHFFFAOYSA-N 0.000 description 1
- JBYKCFLLZLHPIR-UHFFFAOYSA-N 1-ethenoxy-2-ethylsulfanylethane Chemical compound CCSCCOC=C JBYKCFLLZLHPIR-UHFFFAOYSA-N 0.000 description 1
- GXZPMXGRNUXGHN-UHFFFAOYSA-N 1-ethenoxy-2-methoxyethane Chemical compound COCCOC=C GXZPMXGRNUXGHN-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical class CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical class CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 1
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 1
- UULPGUKSBAXNJN-UHFFFAOYSA-N 1-ethenyl-4-phenoxybenzene Chemical compound C1=CC(C=C)=CC=C1OC1=CC=CC=C1 UULPGUKSBAXNJN-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- CTXUTPWZJZHRJC-UHFFFAOYSA-N 1-ethenylpyrrole Chemical compound C=CN1C=CC=C1 CTXUTPWZJZHRJC-UHFFFAOYSA-N 0.000 description 1
- HQSMEHLVLOGBCK-UHFFFAOYSA-N 1-ethenylsulfinylethene Chemical compound C=CS(=O)C=C HQSMEHLVLOGBCK-UHFFFAOYSA-N 0.000 description 1
- BJEWLOAZFAGNPE-UHFFFAOYSA-N 1-ethenylsulfonylethane Chemical compound CCS(=O)(=O)C=C BJEWLOAZFAGNPE-UHFFFAOYSA-N 0.000 description 1
- PAUHLEIGHAUFAK-UHFFFAOYSA-N 1-isocyanato-1-[(1-isocyanatocyclohexyl)methyl]cyclohexane Chemical compound C1CCCCC1(N=C=O)CC1(N=C=O)CCCCC1 PAUHLEIGHAUFAK-UHFFFAOYSA-N 0.000 description 1
- ICLCCFKUSALICQ-UHFFFAOYSA-N 1-isocyanato-4-(4-isocyanato-3-methylphenyl)-2-methylbenzene Chemical compound C1=C(N=C=O)C(C)=CC(C=2C=C(C)C(N=C=O)=CC=2)=C1 ICLCCFKUSALICQ-UHFFFAOYSA-N 0.000 description 1
- DTZHXCBUWSTOPO-UHFFFAOYSA-N 1-isocyanato-4-[(4-isocyanato-3-methylphenyl)methyl]-2-methylbenzene Chemical compound C1=C(N=C=O)C(C)=CC(CC=2C=C(C)C(N=C=O)=CC=2)=C1 DTZHXCBUWSTOPO-UHFFFAOYSA-N 0.000 description 1
- KOCUMXQOUWPSLK-UHFFFAOYSA-N 1-methoxybuta-1,3-diene Chemical compound COC=CC=C KOCUMXQOUWPSLK-UHFFFAOYSA-N 0.000 description 1
- AXFVIWBTKYFOCY-UHFFFAOYSA-N 1-n,1-n,3-n,3-n-tetramethylbutane-1,3-diamine Chemical compound CN(C)C(C)CCN(C)C AXFVIWBTKYFOCY-UHFFFAOYSA-N 0.000 description 1
- CVBUKMMMRLOKQR-UHFFFAOYSA-N 1-phenylbutane-1,3-dione Chemical compound CC(=O)CC(=O)C1=CC=CC=C1 CVBUKMMMRLOKQR-UHFFFAOYSA-N 0.000 description 1
- KUIZKZHDMPERHR-UHFFFAOYSA-N 1-phenylprop-2-en-1-one Chemical compound C=CC(=O)C1=CC=CC=C1 KUIZKZHDMPERHR-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- BEWCNXNIQCLWHP-UHFFFAOYSA-N 2-(tert-butylamino)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCNC(C)(C)C BEWCNXNIQCLWHP-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- MENUHMSZHZBYMK-UHFFFAOYSA-N 2-cyclohexylethenylbenzene Chemical compound C1CCCCC1C=CC1=CC=CC=C1 MENUHMSZHZBYMK-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- SAFZQLDSMLNONX-UHFFFAOYSA-N 2-phenoxyethenylbenzene Chemical compound C=1C=CC=CC=1OC=CC1=CC=CC=C1 SAFZQLDSMLNONX-UHFFFAOYSA-N 0.000 description 1
- FMFHUEMLVAIBFI-UHFFFAOYSA-N 2-phenylethenyl acetate Chemical compound CC(=O)OC=CC1=CC=CC=C1 FMFHUEMLVAIBFI-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- QZWKEPYTBWZJJA-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine-4,4'-diisocyanate Chemical compound C1=C(N=C=O)C(OC)=CC(C=2C=C(OC)C(N=C=O)=CC=2)=C1 QZWKEPYTBWZJJA-UHFFFAOYSA-N 0.000 description 1
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- KHJNXCATZZIGAX-UHFFFAOYSA-N tert-butyl 2-ethyl-2-methylheptaneperoxoate Chemical compound CCCCCC(C)(CC)C(=O)OOC(C)(C)C KHJNXCATZZIGAX-UHFFFAOYSA-N 0.000 description 1
- PFBLRDXPNUJYJM-UHFFFAOYSA-N tert-butyl 2-methylpropaneperoxoate Chemical compound CC(C)C(=O)OOC(C)(C)C PFBLRDXPNUJYJM-UHFFFAOYSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- FUSUHKVFWTUUBE-UHFFFAOYSA-N vinyl methyl ketone Natural products CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
- C08G18/636—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers characterised by the presence of a dispersion-stabiliser
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
- C08G18/638—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers characterised by the use of compounds having carbon-to-carbon double bonds other than styrene and/or olefinic nitriles
Definitions
- the invention relates to the synthesis and use of polyacrylate graft-polyols, and, in one aspect, more particularly relates to polyacrylate graft-polyols useful as dispersants, made by polymerizing at least one acrylate monomer or polymer in a polyol where the resultant polyacrylate is soluble in the polyol employed.
- polystyrene foams The use of a polyol in the preparation of polyurethanes by reaction of the polyol with a polyisocyanate in the presence of a catalyst and perhaps other ingredients is well known.
- Conventional polyols for flexible polyurethane foams such as slab urethane foams, are usually made by the reaction of a polyhydric alcohol with an alkylene oxide, usually ethylene oxide and/or propylene oxide, to a molecular weight of about 2,000 to 5,000 and above. These polyols are then reacted with polyisocyanate in the presence of water or other blowing agents such as fluorocarbons to obtain polyurethane foams.
- Polyols have been modified in many ways in attempts to improve the properties of the resulting polyurethane, for example, by using a polymer polyol as the polyol component.
- Conventional polyols may be used as the dispersing media or base polyol in these polymer polyols.
- dispersions of polymers of vinyl compounds such as styrene, acrylonitrile or a mixture of the two (abbreviated as SAN monomers), or of polyurea polymers, such as those prepared from toluene diisocyanate (TDI) and hydrazine in conventional polyols have been included to improve the properties of the polyols, and thus, the properties of the resulting foam.
- Polyurethane foams with higher load bearing properties ILD--indentation load deflection, and CFD--compression force deflection
- polymer polyols could be prepared which would be stable and have low viscosities.
- Stability is important to the storage life of the polyols before they are used to make the polyurethane foams.
- the tendency of polymer polyols to undergo phase separation if they are not stabilized is well known.
- Low viscosities and small particle sizes are also important in a good quality polyol to permit it to be pumped easily in high volume foam producing equipment.
- styrene/acrylonitrile polymer polyols could be synthesized which would have large SAN ratios.
- the substitution of styrene for acrylonitrile in these polymer polyols helps prevent discoloration during the cure of the polyurethane, and also helps improve flame retardability of the resultant foams.
- the stability of the polymer polyols decreases with increasing styrene to acrylonitrile ratios. Viscosity and particle size are also typically adversely affected with high styrene contents.
- U.S. Pat. No. 4,148,840 to Shah and U.S. Pat. No. 4,242,249 to Van Cleve, et al. describe the use of preformed polymer polyols as dispersion stabilizers in the synthesis of SAN dispersion polyols.
- U.S. Pat. No. 4,148,840 describes preformed polymer polyol stabilizers which have a viscosity of less than 40,000 cps at 25° C. These materials are viscous dispersions or semi-solids, which are difficult to work with.
- the polyols suggested therein for the preformed polymer polyol and the final polymer polyol may be the same or different, and may be of a wide variety.
- the monomers were also suggested from a lengthy list, although only SAN copolymers are discussed in detail.
- the preformed stabilizers in U.S. Pat. No. 4,242,249 are graft or addition copolymers having an anchor portion of a polymer or ethylenically unsaturated monomer of a mixture of monomers chemically bonded to a solvatable portion of a propylene oxide polymer, where the preformed stabilizer again has a viscosity in excess of 40,000 cps at 25° C.
- U.S. Pat. Nos. 4,327,005 and 4,334,049 to Ramlow, et al. teach alkylene oxide adducts of styrene/allyl alcohol copolymers as preformed stabilizers for polymer polyols.
- the stabilizer may take the form of a graft copolymer dispersion or a finely divided solid polymer.
- polyacrylate graft-polyols may be useful themselves as dispersants in preparing polymer polyols that have relatively high styrene contents, but which also had good stability, small particle sizes, and low viscosity as well.
- SAN styrene to acrylonitrile
- Still another object of the invention to provide polyacrylate graft-polyols as dispersants for SAN polymer polyols where the dispersant is prepared from simple monomers and conventional polyols, and no unsaturated polyols or further alkoxylation is required in the dispersant preparation.
- stable, low viscosity polymer polyols made by a process of polymerizing, via a free-radical reaction, a vinyl monomer component, in the presence of a polyol mixture comprising a major portion of a base polyol and a minor portion of a polyacrylate graft-polyol as a dispersant, where the polyacrylate graft-polyol dispersant is made by polymerizing at least one acrylate monomer in the presence of a polyol in which the resulting polymer is soluble.
- the stable, low viscosity polymer polyol compositions have a continuous phase, a disperse phase within the continuous phase, and a dispersant for enhancing the stability of the polymer polyol.
- the disperse phase consists of vinyl polymer particles formed by polymerizing an ethylenically unsaturated monomer or mixture of monomers in the continuous phase.
- the continuous phase consists of a first polyoxyalkylene polyether polyol.
- the dispersant is a polyacrylate graft-polyol formed by polymerizing from about 5 to about 90 weight percent of at least one acrylate monomer that is selected from the group consisting of C 1 -C 20 alkyl esters of acrylic and methacrylic acids in from about 95 to about 10 weight percent of a second polyoxyalkylene polyether polyol to form a single phase homogeneous liquid polyacrylate graft-polyol dispersant.
- the polyacrylate graft-polyol dispersant may be employed in an amount sufficient to enhance the stability of the resulting polymer polyol as compared to the stability of the polymer polyol in the absence of the polyacrylate graft-polyol dispersant.
- the polyacrylate graft-polyol dispersants are prepared by the polymerization of at least one acrylate monomer or polymer in a polyol.
- Alternative methods may be employed.
- the polyacrylate graft-polyol dispersant is formed by polymerizing esters of acrylic and methacrylic acid in situ in a polyoxyalkylene polyether polyol to produce the polyacrylate graft-polyol.
- the acrylate monomer used is preferably an ester which can be used singly or in combination, and in one aspect is a C 1 to C 20 alkyl ester of acrylic and methacrylic acids. They may have the formula:
- R is an alkyl group of one to twenty carbon atoms, such as methyl, ethyl propyl, n-butyl, etc.; and R 1 is hydrogen or methyl.
- Particularly suitable acrylate monomers include methyl acrylate, ethyl acrylate, propyl acrylate, N-butyl acrylate, and the like and their mixtures.
- the polyol and the polymer formed therein made from at least one acrylate monomer must be selected such that the acrylate monomer, and any polymer produced therefrom, is soluble in the polyol.
- the polyol used in forming the final stable, low viscosity polymer polyols using a vinyl monomer component such as SAN will be identified as the first polyol.
- the polyol used in the preparation of the dispersant is designated as the second polyol.
- Both the first and second polyols may referred to at various times as "base polyols".
- both the first and second polyols are polyoxyalkylene polyether polyols. They may also be the same or different polyoxyalkylene polyether polyols.
- both the first polyol and the second polyol have a molecular weight of from about 500 to 15,000, preferably from about 2000 to 10,000, and are typically made by the reaction of an initiator having a plurality of reactive hydrogens thereon with one or more alkylene oxides.
- Suitable initiators include, but are not limited to, glycerin, alkanolamines, alkylamines, aryl or aromatic amines, sucrose, sorbitol, trimethylol propane (TMP) ⁇ -methylglucoside, ⁇ -methylglucoside or other methylglucoside, resins of phenol, aniline and mixed phenol aniline, such as methylenedianiline or bisphenol A, Mannich condensates and mixtures thereof, for example.
- TMP trimethylol propane
- the first or second polyol may be made by alkoxylating the initiator with a desired number of moles of an alkylene oxide.
- the alkylene oxide has two to four carbon atoms, and is thus ethylene oxide, propylene oxide, butylene oxide or mixtures of these oxides.
- propylene oxide is particularly preferred.
- the oxides may be mixed upon addition, or may be added to the polyol initiator chain separately to form blocks or caps. In a preferred aspect, a mixture of ethylene oxide and propylene oxide are added to the initiator.
- the alkoxylation may or may not be catalyzed; KOH is a commonly used catalyst, although others may be employed.
- double metal cyanide catalysts may be employed, in particular zinc hexacyanocobaltate, and the polyols may be prepared in accordance with the methods described in U.S. Pat. Nos. 3,029,505; 3,900,518; 3,941,049 and 4,355,100, incorporated by reference herein.
- a reaction temperature of from about 60° to 150° C. is representative for the making of the dispersants, although it will be appreciated that other conditions may be advantageously employed.
- the monomer content relative to the second polyol is in the range of about 5 to 90 wt. % in from about 95 to about 10 wt. % of the second polyol, and is preferably in the range of about 10 to 50 wt. % in from about 90 to about 50 wt. % of the second polyol. It is conceivable that higher molecular weight modified polyols could be prepared by the methods of this invention.
- SAN ratios that can be supported by the polymer polyols of the present invention using polyacrylate graft-polyol dispersants range from greater than 60/40 to about 85/15, more commonly being in the range of about 65/35 to about 75/25.
- the viscosities available with the method of this invention are less than those made using only polyoxylalkylene polyether polyols as the base polyol with no dispersant. A smaller average particle size of the dispersed solid is also obtained, as well as enhanced dispersion stability.
- the base polyol has already been described.
- the base or first polyol is the major portion of the polyol material used, whereas the dispersant is a minor portion of the total polyol material used.
- the weight percentage of dispersant to the total of (1) the base polyol (including all portions, if multiple proportions are used), (2) the dispersant and (3) the monomer proportion ranges from about 0.1 to about 20 weight percent, and preferably from about 1 to about 15 weight percent.
- the reactor may be a batch reactor, a semi-batch reactor or one or more continuous stirred tank reactors (CSTRs). A process which is capable of maintaining high agitation and a low monomer to polyol ratio throughout the process is preferred.
- all of the dispersant is added in the reactor charge, and it is preferred that a majority of the dispersant is added in the reactor charge. In turn, it is preferred that a majority of the polyol employed be added in the feed stream, rather than the reactor charge.
- a plurality of CSTR reactors in series could be employed if the feed to the first CSTR had the higher dispersant proportion fed to it and its product fed into a second CSTR which also received the feed stream.
- a relatively high concentration of dispersant is preferably initially charged to the reactor to achieve the polymer polyols of the present invention.
- the preferred dispersants of this invention are expected to produce polymer polyols at solid levels of up to 40%, and perhaps higher. Typically, these solids levels range from about 15-30%.
- the preparation of the polymer polyols of the present invention may be performed by polymerizing an ethylenically unsaturated monomer or mixture of monomers in a polyol mixture comprising at least one polyoxyalkylene polyol and a polyacrylate graft-polyol dispersant in the presence of a free radical initiator at a temperature in the range of 60° to 150° C., preferably in the range of about 100° to 130° C.
- any suitable addition time of the feed stream to the reactor contents may be employed, for example, the addition time may range from 0.5 to 4.0 hours, preferably 1 to 2.5 hours.
- the proportion of the polymerization initiator as a wt. % of the total reactants may range from 0.05 to 5.0 wt. %, preferably 0.1 to 1.0 wt. %.
- the weight ratio of total monomer or monomer mixture (or disperse phase) to polyol (or continuous phase) will be from about 1:19 to about 9:11.
- the preferred monomers employed in the method and polymer polyols of the present invention are both styrene and acrylonitrile to make a copolymer.
- the relative proportions of styrene to acrylonitrile, the SAN ratio has been discussed above and will be exemplified below, although it is anticipated that SAN ratios of up to 85/15 may be developed in some aspects of this invention.
- Suitable monomers include, but are not limited to, butadiene, isoprene, 1,4-pentadiene, 1,6-hexadiene, 1,7-octadiene, styrene, acrylonitrile, methacrylonitrile, ⁇ -methylstyrene, methylstyrene, 2,4-dimethylstyrene, ethyl styrene, isopropylstyrene, butylstyrene, substituted styrenes, such as cyanostyrene, phenylstyrene, cyclohexylstyrene, benzylstyrene, substituted styrenes such as cyanostyrene, nitrostryrene, N,N-dimethylaminostyrene, acetoxystyrene, methyl 4-vinylbenzoate, phenoxystyrene, p-
- the polymerization initiator may be any suitable initiator for the particular monomers employed.
- Suitable catalytic initiators useful in producing the polymer polyol compositions of this invention are the free radical type of vinyl polymerization catalysts, such as the peroxides, persulfates, perborates, percarbonates, azo compounds, and the like.
- Viscosities were measured using a Brookfield cone and plate viscometer, Spindle #CP-52, operated at 20 secs -1 at 25° C.
- Particle sizes were measured using a Coulter N4 Particle Size Analyzer with o-xylene or isopropyl alcohol as the dispersing media.
- Centrifugable solids were determined by centrifuging a sample of the polymer polyol for about 24 hours at about 3300 rpm and 1470 radial centrifugal "g" forces. The centrifuge tube was then inverted and allowed to drain for 4 hours. The non-flowing cake at the bottom of the tube is reported as weight percent of the initial weight of the sample tested.
- the preparation of the polyacrylate dispersants of the present invention were conducted according to the following procedure unless otherwise noted.
- the initiator was Vazo 67, and the digestion time was 0.5 hours.
- the formulations give good polymer polyols at a SAN ratios of up to 75/25. Higher ratios could be expected with more optimization. Note also that the resulting polymer polyols have relatively low viscosities.
- the polymer polyol of Example 14 in particular has a high solids content of 40 wt. %.
- the polymer polyols prepared in accordance with the above examples may then be incorporated into a formulation which results in a polyurethane product.
- the polymer polyol of the invention may be used in conjunction with a polyisocyanate or may be combined with additional polyols well known in the art, and reacted with a polyisocyanate to form a slab polyurethane foam product.
- polyurethane foams are produced. It will be shown that the polymer polyols of the present invention may also be blended with conventional polyols.
- a catalyst useful in preparing foams of this type is employed in the usual manner.
- Such catalyst may include those mentioned above, or one or more of the following:
- Tertiary amines such as trimethylamine, triethylamine, N-methylmorpholine, N-ethylmorpholine, N,N-dimethylbenzylamine, N,N-diemethylethanolamine, N,N,N',N'-tetramethyl-1,3-butanediamine, N,N-dimethylpiperazine, 1,4-diazobicyclo[2.2.2.]octane and the like;
- Acidic metal salts of strong acids such as ferric chloride, stannic chloride, stannous chloride, antimony trichloride, bismuth nitrate and chloride, and the like;
- Chelates of various metals such as those which can be obtained from acetylacetone, benzoylacetone, trifluoroacetyl acetone, ethyl acetoacetate, salicyclaldehyde, cyclopentanone-1-carboxylate, acetylacetoneimine, bisacetylacetonealkylenediamines, salicyclaldehydeimine, and the like, with various metals such as Be, Mg, Zn, Cd, Pd, Ti, Zr, Sn, As, Bi, Cr, Mo, Mn, Fe, Co, and Ni;
- Alcoholates and phenolates of various metals such as Ti(OR) 4 , Sn(OR) 4 , Al(OR) 3 , and the like, wherein R is alkyl or aryl, and the reaction products of alcoholates with carboxylic acids, beta-diketones, and 2-(N,N-dialkylamino)alkanols;
- salts of organic acids with a variety of metals such as alkali metals, alkaline earth metals, Al, Sn, Pb, Mn, Co, Ni, and Cu, including, for example, sodium acetate, stannous octoate, stannous oleate, lead octoate, metallic driers such as manganese and cobalt naphthenate, and the like; and
- the amount of catalyst employed ranges from about 0.01 to about 5.0 parts by weight percent based on 100 parts by weight of the polyol. More often the amount of catalyst used is 0.2 to 2.0 parts by weight.
- the polyol component for the polyurethane foam is reacted in the presence of one or more of the above catalysts with a polyisocyanate according to conventional procedures.
- the polyisocyanate used may be any aromatic or aliphatic polyisocyanate, such as toluene diisocyanates, polymeric isocyanates and aliphatic diisocyanates.
- Typical aromatic polyisocyanates include, but are not limited to, m-phenylene diisocyanate, p-phenylene diisocyanate, polymethylene polyphenylisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, dianisidine diisocyanate, bitolylene diisocyanate, naphthalene-1,4-diisocyanate, diphenylene-4,4'-diisocyanate, aliphatic-aromatic diisocyanates, such as xylylene-1,4-diisocyanate, xylylene-1,2-diisocyanate, xylylene-1,3-diisocyanate, bis(4-isocyanatophenyl)-methane, bis(3-methyl-4-isocyanatophenyl)methane, and 4,4'-diphenylpropane diisocyanate.
- Suitable aliphatic diisocyanates would include isophorone diisocyanate, hexamethylene diisocyanate and methylene-bis-cyclohexylisocyanate. Toluene diisocyanates are preferred.
- Aromatic polyisocyanates suitable for use include methylene-bridged polyphenyl polyisocyanate mixtures which have a functionality of from about 2 to about 4. These latter isocyanate compounds are generally produced by the phosgenation of corresponding methylene bridged polyphenyl polyamines, which are conventionally produced by the reaction of formaldehyde and primary aromatic amines, such as aniline, in the presence of hydrochloric acid and/or other acidic catalysts.
- Known processes for preparing the methylene-bridged polyphenyl polyisocyanates and corresponding methylene-bridged polyphenyl polyisocyanates therefrom are described in the literature and in many patents: for example, U.S. Pat. Nos. 2,683,730; 2,950,263; 3,012,008; 3,344,162; and 3,362,979.
- the most preferred methylene-bridged polyphenyl polyisocyanate mixtures used here contain from about 20 to about 100 wt. % methylene diphenyl diisocyanate isomers with the remainder being polymethylene polyphenyl diisocyanates having higher functionalities and higher molecular weights.
- Typical of these are polyphenyl polyisocyanate mixtures containing about 20 to 100 wt. % methylene diphenyl diisocyanate isomers, of which 20 to about 95 wt. % thereof is the 4,4'-isomer with the remainder being polymethylene polyphenyl polyisocyanates of higher molecular weight and functionality that have an average functionality of from about 2.1 to about 3.5.
- the isocyanate mixtures are known, commercially available materials and can be prepared by the process described in U.S. Pat. No. 3,362,979, issued Jan. 9, 1968 to Floyd E. Bentley.
- Foaming is carried out in the presence of water and, optionally, additional organic blowing agents.
- the water is normally used in amounts of 0.5 to 15 parts by weight, preferably, 1.0 to 10 parts by weight (pbw) based on 100 parts by weight of the polymer polyol and any additional polyol present.
- the organic blowing agents optionally used along with the water are known in the art and are, for example, monofluorotrichloromethane, difluorodichloromethane, methylene dichloride and others generally known in the art.
- Additives to regulate the cell size and the cell structure for example, silicone surfactant such as dimethylpolysiloxanes, may also be added to the foaming mixture. Fillers, flame retarding additives, dyes or plasticizers of known types may also be used. These and other additives are well known to those skilled in the art.
- the polyurethane foam was separately prepared by charging the amounts of polyol, polymer polyol, water, catalysts, silicone surfactant, and flame retardant compound indicated into a one-liter cylindrical container equipped with a mechanical stirrer. The mixture was stirred for about 30 seconds at about 2500 rpm, and the indicated amount of polyisocyanate was introduced into the container with stirring for about 10 seconds. The contents of the container were then immediately poured into a cardboard cake box and the foam was allowed to rise. After the foam rise was completed, the foam was allowed to cure at room temperature for about one week.
- polyacrylate graft-polyol dispersants in the preparation of polymer polyols results in the ability to use higher SAN weight ratios, and higher polymer solids contents along with acceptable viscosities.
- the use of polyacrylate graft-polyols as dispersants results in polymer polyols having higher styrene contents, and improved stability and viscosity properties.
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
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- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Description
CH.sub.2 ═CR.sup.1 CO.sub.2 R
TABLE I __________________________________________________________________________ PREPARATION OF POLYACRYLATE GRAFT-POLYOL DISPERSANTS Example No. 1 2 3 4 5 6 7 __________________________________________________________________________ Monomer Ethyl Acrylate/ → → → → n-Butyl .sup.1 Composition n-Butyl Acrylate Acrylate Monomer Wt. 50/50 50/50 50/50 50/50 50/50 100 37.5/37.5/25 Ratio Base Polyol ARCOL .sup.® 5613 ARCOL 1130 Thanol .sup.® SF-5505 Thanol SF-5507 .sup.2 ARCOL 1130 ARCOL 1130 Reaction 122 123 121 123 122 120 120 Temp., °C. Initiator Conc., 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Wt. % Feed, Addition 1.0 1.5 1.5 1.5 1.75 1.5 1.5 Time, hr. Reactor 100 100 100 100 100 100 100 Charge, g. Base Polyol Feed Charge, g. Monomers 400 400 400 400 400 400 400 VAZO 67 10.0 10.0 10.0 10.0 10.0 10.0 10.0 Base Polyol 500 500 500 500 500 500 500 Monomer 97 94 97 96 93 96 95 Conv., % Viscosity, cps, 2950 2950 5110 8300 18,200 1810 8160 5/sec __________________________________________________________________________ .sup.1 Ethyl Acrylate/nButyl Acrylate/ Methyl Methacrylate .sup.2 A glycerin initiated polyether of propylene oxide capped with ethylene oxide containing 7% ethylene oxide and having a hydroxyl number of 16 and an unsaturation content of 0.010 meq/g.
TABLE II __________________________________________________________________________ PREPARATION OF POLYMER POLYOLS Example No. 8 9 10 11 12 13 14 __________________________________________________________________________ Monomer Charge Wt. % 20 20 20 30 30 35 40 SAN Weight Ratio 75/25 75/25 75/25 70/30 70/30 70/30 70/30 Base Polyol ARCOL .sup.® 5613 → → → → → → Dispersant from Ex. 1 1 1 1 5 5 5 % of Total Polyol Feed 88 94 94 93 94 94 93 Reaction Temp., °C. 120 120 120 120 120 120 120 Initiator Conc., Wt. % 0.5 0.5 0.5 0.5 0.5 0.6 0.69 Feed, Addition Time, hr. 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Feed Charge, g. Styrene 300 300 300 420 420 490 560 Acrylonitrile 100 100 100 180 180 210 240 VAZO 67 10.0 10.0 10.0 10.0 10.0 12.0 13.7 Base Polyol 1400 1500 1500 1300 1316 1221 1120 Reactor Charge, g. Base Polyol -- -- 50 -- 42 40 40 Dispersant 200 100 50 100 42 39 36 Polymer Polyol Properties Overall Monomer Conv., % 95 94 94 96 96 97 98 Viscosity, cps, 1400 1180 1240 2510 2240 3460 7340 Particle Size, μ 0.93 1.22 2.06 1.95 1.04 1.08 1.32 Centrifugable Solids, Wt. % 2.5 6.5 12.1 8.9 2.2 3.0 14.6 __________________________________________________________________________
TABLE III __________________________________________________________________________ PREPARATION OF POLYMER POLYOLS Example No. 15 16 17 18 __________________________________________________________________________ Monomer Charge Wt. % 20 20 20 20 SAN Weight Ratio 70/30 75/25 70/30 75/25 Base Polyol ARCOL .sup.® 1130 → → Thanol .sup.® SF-5505 Dispersant from Ex. 2 2 2 3 % of Total Polyol Feed 94 94 88 90 Reaction Temp., °C. 120 120 120 120 Initiator Conc., Wt. % 0.5 0.5 0.5 0.25 Feed, Addition Time, hr. 2.0 2.0 2.0 2.0 Feed Charge, g. Styrene 280 300 280 300 Acrylonitrile 120 100 120 100 VAZO 67 10.0 10.0 10.0 5.0 Base Polyol 1500 1500 1400 1440 Reactor Charge, g. Base Polyol -- -- -- 100 Dispersant 100 100 200 60 Polymer Polyol Properties Overall Monomer Conv., % 91 90 93 93 Viscosity, cps, 1380 1190 1480 2280 Particle Size, μ 1.00 0.93 0.67 1.00 Centrifugable Solids, Wt. % 2.2 9.1 1.8 3.0 __________________________________________________________________________
______________________________________ FORMULATION parts by wt. ______________________________________ ARCOL .sup.® 1130 60 Polymer Polyol 40 Water 4.2 Niax 5750 Surfactant.sup.1 1 Niax A-200 Catalyst.sup.2 0.23 T-9 Catalyst.sup.3 0.15 Thermolin 101 Flame Retardant.sup.4 10 TDI Index 108 ______________________________________ .sup.1 Silicon surfactant, made by Union Carbide Corp. .sup.2 Amine catalyst, made by Union Carbide Corp. .sup.3 Organotin catalyst, made by Air Products and Chemicals, Inc. .sup.4 Tetrakis(2-Chloroethyl)Ethylene Diphosphate, made by Olin Corporation
TABLE III ______________________________________ Slab Polyurethane Foam Preparation Foam Example No. 19 20 ______________________________________ Polymer Polyol # 15 17 Foam Reactivity Cream Time, sec. 7 7 Peak Rate, in./min. 0.75 0.79 Cell Openness, % 80 80 Density, PCF (lb./ft.sup.3) 1.88 1.77 Air Flow, CFM (ft.sup.3 /min.) 2.57 2.93 Tensile Strength, PSI (lb./in..sup.2) 14.3 15.1 Elongation, % 134 158 Tear Strength, PLI (lb./linear in.) 1.69 2.43 Compression Set, 90% 12 11.3 HACS.sup.1, 90% 10.2 11.9 CFD, 25% 0.615 0.53 CFD, 40% 0.66 0.56 CFD, 65% 1.18 0.98 CFD, 25% Ret. 0.415 0.35 GCFD.sup.2, 25% 0.33 0.30 Sag Factor 1.92 1.85 Recovery, % 67.48 66.04 ______________________________________ .sup.1 Humid Age Compression Set .sup.2 Guide Compression Force Deflection
GLOSSARY ______________________________________ ARCOL .sup.® 1130 A glycerin initiated polyether of propylene oxide and ethylene oxide having a hydroxyl number of 48 and containing essentially secondary hydroxyl groups, made by ARCO Chemical Company. ARCOL 5613 A glycerin initiated polyether of propylene oxide and ethylene oxide having a hydroxyl number of 56 and containing essentially secondary hydroxyl groups, made by ARCO Chemical Company. THANOL .sup.® SF-5505 A glycerin initiated polyether of propylene oxide and ethylene oxide with a hydroxyl number of 34 and a primary hydroxyl group content of 80% based on the total hydroxyl content of the polyether, made by ARCO Chemical Company. THANOL SF-5507 A glycerin initiated polyether of propylene oxide and ehtylene oxide modified with the diglycidyl ether of bisphenol A, with a hydroxyl number of 34 and a primary hydroxyl group content of 80% based on total hydroxyl content of the polyether, made by ARCO Chemical Company. Vazo 67 2,2'-Azobis(2-methylbutanenitrile) polymerization catalyst made by E. I. duPont de Nemours and Co. ______________________________________
Claims (36)
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/226,329 US5070141A (en) | 1988-07-29 | 1988-07-29 | Polyacrylate graft-polyol dispersants |
ES89307657T ES2060774T3 (en) | 1988-07-29 | 1989-07-27 | POLYOL DISPERSANTS GRAFTED WITH POLYACRYLATES. |
DE68918528T DE68918528T2 (en) | 1988-07-29 | 1989-07-27 | Polyacrylate-grafted polyol dispersants. |
EP89307657A EP0353071B1 (en) | 1988-07-29 | 1989-07-27 | Polyacrylate graft-polyol dispersants |
JP1194457A JPH0286609A (en) | 1988-07-29 | 1989-07-28 | Polyacrylate-grafted polyol dispersant |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/226,329 US5070141A (en) | 1988-07-29 | 1988-07-29 | Polyacrylate graft-polyol dispersants |
Publications (1)
Publication Number | Publication Date |
---|---|
US5070141A true US5070141A (en) | 1991-12-03 |
Family
ID=22848500
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US07/226,329 Expired - Fee Related US5070141A (en) | 1988-07-29 | 1988-07-29 | Polyacrylate graft-polyol dispersants |
Country Status (5)
Country | Link |
---|---|
US (1) | US5070141A (en) |
EP (1) | EP0353071B1 (en) |
JP (1) | JPH0286609A (en) |
DE (1) | DE68918528T2 (en) |
ES (1) | ES2060774T3 (en) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5194493A (en) * | 1989-06-16 | 1993-03-16 | Hayes John E | Polymer polyol composition containing a grafted polyol-polyacrylate dispersant |
US5225481A (en) * | 1988-07-29 | 1993-07-06 | Arco Chemical Technology, L.P. | Polyol polyacrylate dispersants |
US6624209B2 (en) | 1999-07-30 | 2003-09-23 | Sanyo Chemical Industries, Ltd. | Polymer polyol composition, process for producing the same, and process for producing polyurethane resin |
US6756414B2 (en) | 1999-07-30 | 2004-06-29 | Sanyo Chemical Industries, Ltd. | Polymer polyol composition, process for producing the same, and process for producing polyurethane resin |
US20050154173A1 (en) * | 2004-01-13 | 2005-07-14 | Beach Bradley L. | Polyurethane elastomers with combination of curatives |
US20050154149A1 (en) * | 2004-01-13 | 2005-07-14 | Beach Bradley L. | Polyurethane rolls and methods of manufacturing |
US20050154174A1 (en) * | 2004-01-13 | 2005-07-14 | Killeen Kelly A. | Graft polymer curatives and polyurethanes formed therefrom |
US7166358B2 (en) | 2004-01-13 | 2007-01-23 | Lexmark International, Inc. | Polyurethane rolls with graft polyacrylate curatives |
EP1939231A1 (en) * | 2005-09-02 | 2008-07-02 | Mitsui Chemicals Polyurethanes, Inc. | (meth)acylate-grafted polyether polyol, and process for production and use thereof |
US8470927B2 (en) | 2004-02-26 | 2013-06-25 | Bayer Materialscience Llc | Process for production of polymer polyols |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2767881B2 (en) * | 1989-05-10 | 1998-06-18 | 旭硝子株式会社 | Method for producing polymer-dispersed polyol and polyurethane |
CA2018186C (en) * | 1989-06-16 | 2001-08-14 | John E. Hayes | Polymer polyol composition containing a grafted polyol-polyacrylate dispersant |
GB9710772D0 (en) * | 1997-05-23 | 1997-07-23 | Dow Europ Sa | Polymer polyol compositions having grafted unsaturated acid salt and their use in the preparation of polyurethane foams |
CN114989369B (en) * | 2022-05-06 | 2023-10-20 | 万华化学集团股份有限公司 | Heat-resistant SAN copolymer and preparation method and application thereof |
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EP1939231A1 (en) * | 2005-09-02 | 2008-07-02 | Mitsui Chemicals Polyurethanes, Inc. | (meth)acylate-grafted polyether polyol, and process for production and use thereof |
US20090111952A1 (en) * | 2005-09-02 | 2009-04-30 | Mitsui Chemicals Polyurethanes, Inc. | (Meth)acrylate-grafted polyether polyol, and production process and use thereof |
EP1939231A4 (en) * | 2005-09-02 | 2009-08-26 | Mitsui Chemicals Polyurethanes | (meth)acylate-grafted polyether polyol, and process for production and use thereof |
Also Published As
Publication number | Publication date |
---|---|
JPH0286609A (en) | 1990-03-27 |
EP0353071A3 (en) | 1990-10-17 |
EP0353071B1 (en) | 1994-09-28 |
EP0353071A2 (en) | 1990-01-31 |
DE68918528D1 (en) | 1994-11-03 |
ES2060774T3 (en) | 1994-12-01 |
DE68918528T2 (en) | 1995-01-26 |
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